Introduction to Chemical Kinetics

An Introduction to Chemical Kinetics provides a gentle overview of the subject offering a comprehensive coverage of key topics needed for a clear understanding of the fundamental aspects of kinetics. Emphasis is placed on how experimental data is collected and manipulated to give standard kinetic quantities relating to rates of reaction. The book then moves on to interpret these quantities, and to develop mechanisms describing the chemical steps in a wide variety of reactions in both gas and solution phase.The student is carefully guided through the necessary theory, in particular looking at how and why reactions occur and the physical and chemical requirements for reaction.
An invaluable text for students of chemistry, chemical engineering, pharmacy and biochemistry taking a first course in kinetics. This book will also be of interest to professionals in the chemical and pharmaceutical industry needing an accessible introduction to the subject.Includes learning objectives, summary sections and end of chapter problems.Step by step guidance and and clear explanation of topics.Includes a wide variety of worked examples throughout.Shows the relevance of kinetics to many areas of chemistry.

Spis treści:
Preface.
List of Symbols.
1. Introduction.
2. Experimental Procedures.
2.1 Detection, Identification and Estimation of Concentration of Species Present.
2.1.1 Chromatographic techniques: liquid–liquid and gas–liquid chromatography.
2.1.2 Mass spectrometry (MS).
2.1.3 Spectroscopic techniques.
2.1.4 Lasers.
2.1.5 Fluorescence.
2.1.6 Spin resonance methods: nuclear magnetic resonance (NMR).
2.1.7 Spin resonance methods: electron spin resonance (ESR).
2.1.8 Photoelectron spectroscopy and X–ray photoelectron spectroscopy.
2.2 Measuring the Rate of a Reaction.
2.2.1 Classification of reaction rates.
2.2.2 Factors affecting the rate of reaction .
2.2.3 Common experimental features for all reactions.
2.2.4 Methods of initiation.
2.3 Conventional Methods of Following a Reaction.
2.3.1 Chemical methods.
2.3.2 Physical methods.
2.4 Fast Reactions.
2.4.1 Continuous flow.
2.4.2 Stopped flow.
2.4.3 Accelerated flow.
2.4.4 Some features of flow methods.
2.5 Relaxation Methods.
2.5.1 Large perturbations.
2.5.2 Flash photolysis.
2.5.3 Laser photolysis.
2.5.4 Pulsed radiolysis.
2.5.5 Shock tubes.
2.5.6 Small perturbations: temperature, pressure and electric field jumps.
2.6 Periodic Relaxation Techniques: Ultrasonics.
2.7 Line Broadening in NMR and ESR Spectra.
Further Reading.
Further Problems.
3. The Kinetic Analysis of Experimental Data.
3.1 The Experimental Data.
3.2 Dependence of Rate on Concentration.
3.3 Meaning of the Rate Expression.
3.4 Units of the Rate Constant, k.
3.5 The Significance of the Rate Constant as Opposed to the Rate.
3.6 Determining the Order and Rate Constant from Experimental Data.
3.7 Systematic Ways of Finding the Order and Rate Constant from Rate/Concentration Data.
3.7.1 A straightforward graphical method.
3.7.2 log/log Graphical procedures.
3.7.3 A systematic numerical procedure.
3.8 Drawbacks of the Rate/Concentration Methods of Analysis.
3.9 Integrated Rate Expressions.
3.9.1 Half–lives.
3.10 First Order Reactions.
3.10.1 The half–life for a first order reaction.
3.10.2 An extra point about first order reactions.
3.11 Second Order Reactions.
3.11.1 The half–life for a second order reaction.
3.11.2 An extra point about second order reactions.
3.12 Zero Order Reaction.
3.12.1 The half–life for a zero order reaction.
3.13 Integrated Rate Expressions for Other Orders.
3.14 Main Features of Integrated Rate Equations.
3.15 Pseudo–order Reactions.
3.15.1 Application of pseudo–order techniques to rate/concentr ation data.
3.16 Determination of the Product Concentration at Various Times.
3.17 Expressing the Rate in Terms of Reactants or Products for Non–simple Stoichiometry.
3.18 The Kinetic Analysis for Complex Reactions.
3.18.1 Relatively simple reactions that are mathematically complex.
3.18.2 Analysis of the simple scheme A—!
3.18.3 Two conceivable situations.
3.19 The Steady State Assumption.
3.19.1 Using this assumption.
3.20 General Treatment for Solving Steady States.
3.21 Reversible Reactions.
3.21.1 Extension to other equilibria.
3.22 Pre–equilibria.
3.23 Dependence of Rate on Temperature.
Further Reading.
Further Problems.
4. Theories of Chemical Reactions.
4.1 Collision Theory.
4.1.1 Definition of a collision in simple collision theory.
4.1.2 Formulation of the total collision rate.
4.1.3 The p factor.
4.1.4 Reaction between like molecules.
4.2 Modified Collision Theory.
4.2.1 A new definition of a collision.
4.2.2 Reactive collisions.
4.2.3 Contour diagrams for scattering of products of a reaction.
4.2.4 Forward scattering: the stripping or grazing mechanism.
4.2.5 Backward scattering: the rebound mechanism.
4.2.6 Scattering diagrams for long–lived complexes.
4.3 Transition State Theory.
4.3.1 Transition state theory, configuration and potential energy.
4.3.2 Properties of the potential energy surface relevant to transition state theory.
4.3.3 An outline of arguments involved in the derivation of the rate equation.
4.3.4 Use of the statistical mechanical form of transition state theory.
4.3.5 Comparisons with collision theory and experimental data.
4.4 Thermodynamic Formulations of Transition State Theory.
4.4.1 Determination of thermodynamic functions for activation.
4.4.2 Comparison of collision theory, the partition function form and the thermodynamic form of transition state theory.
4.4.3 Typical approximate valu es of contributions entering the sign and magnitude of —S61/4—.
4.5 Unimolecular Theory.
4.5.1 Manipulation of experimental results.
4.5.2 Physical significance of the constancy or otherwise of k1, k—1 and k2.
4.5.3 Physical significance of the critical energy in unimolecular reactions.
4.5.4 Physical significance of the rate constants k1, k—1 and k2.
4.5.5 The simple model: that of Lindemann.
4.5.6 Quantifying the simple model.
4.5.7 A more complex model: that of Hinshelwood.
4.5.8 Quantifying Hinshelwood′s theory.
4.5.9 Critique of Hinshelwood′s theory.
4.5.10 An even more complex model: that of Kassel.
4.5.11 Critique of the Kassel theory.
4.5.12 Energy transfer in the activation step.
4.6 The Slater Theory.
Further Reading.
Further Problems.
5. Potential Energy Surfaces.
5.1 The Symmetrical Potential Energy Barrier.
5.2 The Early Barrier.
5.3 The Late Barrier.
5.4 Types of Elementary Reaction Studied.
5.5 General Features of Early Potential Energy Barriers for Exothermic Reactions.
5.6 General Features of Late Potential Energy Surfaces for Exothermic Reactions.
5.6.1 General features of late potential energy surfaces where the attacking atom is light.
5.6.2 General features of late potential energy surfaces for exothermic reactions where the attacking atom is heavy.
5.7 Endothermic Reactions.
5.8 Reactions with a Collision Complex and a Potential Energy Well
Further Reading.
Further Problems.
6. Complex Reactions in the Gas Phase.
6.1 Elementary and Complex Reactions.
6.2 Intermediates in Complex Reactions.
6.3 Experimental Data.
6.4 Mechanistic Analysis of Complex Non–chain Reactions.
6.5 Kinetic Analysis of a Postulated Mechanism: Use of the Steady State Treatment.
6.5.1 A further example where disentangling of the kinetic data is necessary.
6.6 Kinetically Equivalent Mechanisms.
6.7 A Compar